System for DMS peak resolution

ABSTRACT

An apparatus for identification of chemical species by measurement of mobility as a function of high electric field and for generating unique compound-dependent signatures based on ion mobility at a plurality of peak RF voltages for a given compensation. The resulting detection data is compared against a library of data in order to identify a detected chemical species.

RELATED APPLICATION(S)

This application is a continuation-in-part of U.S. application Ser. No.10/187,464, filed Jun. 28, 2002 now U.S Pat. No. 7,045,776 entitled“System For Collection Of Data And Identification Of Unknown Ion SpeciesIn An Electric Field,” which is a continuation-in-part of U.S.application Ser. No. 09/896,536 filed Jun. 30, 2001 now abandonedentitled “Apparatus For Simultaneous Identification Of Multiple ChemicalCompounds;” and claims the benefit of U.S. Provisional Application No.60/340,894 filed Oct. 30, 2001 entitled “Compound Identification ByMobility Dependence On Electric Field,” U.S. Provisional Application No.60/334,670, filed Nov. 15, 2001 now abandoned entitled “System For IonMobility And Polarity Discrimination And Identification Of ChemicalCompounds;” U.S. Provisional Application No. 60/340,904, filed Dec. 12,2001 entitled “System For Ion Mobility And Polarity Discrimination AndIdentification Of Chemical Compounds;” U.S. Provisional Application No.60/342,588 filed Dec. 20, 2001 entitled “Field Dependence Of MobilitiesFor Gas Phase Protonated Monomers And Proton Bound Dimers Of Ketones ByPlanar Field Asymmetric Waveform Ion Mobility Spectrometer (PFAIMS);”and U.S. Provisional Application No. 60/351,043 filed Jan. 23, 2002entitled “Method And Apparatus For FAIMS Detection Of SF6,” all of whichare incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates generally to identification of unknownmembers of a sample by mobility characteristics, and more particularlyto devices that analyze compounds via high field asymmetric waveform ionmobility spectrometry.

There are a number of different circumstances in which it is desirableto perform a chemical analysis to identify compounds in a sample. Suchsamples may be taken directly from the environment or they may beprovided by front end specialized devices to separate or preparecompounds before analysis. Unfortunately, recent events have seenmembers of the general public exposed to dangerous chemical compounds insituations where previously no thought was given to such exposure. Thereexists, therefore, a demand for low cost, accurate, easy to use, andreliable devices capable of detecting the chemical makeup of a sample.

One class of known chemical analysis instruments are mass spectrometers.Mass spectrometers are generally recognized as being the most accuratetype of detectors for compound identification, given that they cangenerate a fingerprint pattern for even fragment ions. However, massspectrometers are quite expensive, easily exceeding a cost of $100,000or more and are physically large enough to become difficult to deployeverywhere the public might be exposed to dangerous chemicals. Massspectrometers also suffer from other shortcomings such as the need tooperate at relatively low pressures, resulting in complex supportsystems. They also need a highly trained operator to tend to andinterpret the results. Accordingly, mass spectrometers are generallydifficult to use outside of laboratories.

A class of chemical analysis instruments more suitable for fieldoperation is known as are known as Field Asymmetric Ion MobilitySpectrometers (FAIMS), also known as Radio Frequency Ion MobilitySpectrometers (RFIMS), and Differential Mobility Spectrometers (DMS),among other names. This type of spectrometer subjects an ionized gassample to a varying high-low asymmetric electric field and filters ionsbased on their field mobility.

The gas sample flows through a field which allows only selected ionspecies to pass through, according to the compensation voltage, andspecifically only those ions that exhibit particular mobility responsesto the field. An ion detector then collects detection intensity data forthe detected ions. The intensity data exhibit attributes such as“peaks.” These peaks are interpreted according to the compensationvoltage at which a species of ion is able to pass through an asymmetricfield of set field parameters.

A typical FAIMS device includes a pair of electrodes in a drift tube. Anasymmetric field is applied to the electrodes across the ion flow path.The asymmetric RF field, as shown in FIG. 1A, alternates between a highor “peak” field strength and a low field strength. The field varies witha particular time period, t, (frequency) and duty cycle d. Fieldstrength, E, varies as the applied voltage V and size of the gap betweenelectrodes. Ions will pass through the gap between the electrodes onlywhen their net transverse displacement per period of the asymmetricfield is zero; in contrast, ions that undergo a net displacement willeventually undergo collisional neutralization on one of the electrodes.In a given Radio Frequency (RF) asymmetric field, a displaced ion can berestored to the center of the gap (i.e. compensated, with no netdisplacement for that ion) when a low strength DC electric field (thecompensation voltage, Vcomp) is superimposed on the RF. Ions withdiffering displacement (owing to characteristic dependence of mobilityin the high field condition) can be passed through the gap atcompensation voltages characteristic of a particular ion and this isaccomplished by applying various strengths of Vcomp. In this case, thissystem can function as continuous ion filter; or a scan of Vcomp willallow complete measure of ion species in the analyzer. The recordedimage of the spectral scan of the sample is sometimes referred to as a“mobility scan” or as an “ionogram”).

Examples of mobility scans based on the output from a FAIMS device areshown in FIGS. 1B-1 and 1B-2. The compounds analyzed here consisted ofacetone and an isomer of xylene (o-xylene). In the first case (FIG.1B-1) a single compound, acetone, was independently applied to the FAIMSanalyzer. The illustrated plot is typical of the observed response ofthe FAIMS device, with an intensity of detected ions dependent on thecompensation voltage (Vcomp). For example, the acetone sample exhibiteda peak intensity response at a compensation voltage of approximately −2volts.

FIG. 1B-2 illustrates the results when analyzing a mixture of the twocompounds, here, acetone and o-xylene. The combined response shows twopeaks in approximately the same region as for the independent case. Thecompounds in the mixture can therefore be detected by comparing theresponse against the library, for example, of stored known responses forindependently analyzed compounds, or libraries of mixtures. Thus, theindependently analyzed compounds shown in FIG. 1B-1 can be stored in acomputer system, and when compound responses such as that in FIG. 1B-2are observed, the relative locations of the peaks can be comparedagainst the stored responses in the library to determine theconstitution of the mixture.

A problem occurs, however, especially with FAIMS devices, in thatrelatively complex samples can be very difficult to detect. First ofall, the peaks as seen in the typical FAIMS spectra are generally broadin width. Therefore, compounds having similar peak compensation voltagesmay therefore be difficult to separate from one another. Indeed, theremay be particular conditions where two different chemicals actuallyexhibit the same compensation voltage at a given maximum intensity forthe applied asymmetric RF voltage (referred to here as peak RF voltage).In such a case, it is not possible to resolve between two differentchemicals at all. Another problem may occur when two or more chemicalspecies have the same or almost the same mobility. This is most likelyto happen in the low electric field regime where most existing ionmobility spectrometer systems operate. Therefore, if two or morechemical species have the same or almost the same mobility, then theirspectroscopic peaks will overlap, and identification and quantificationof individual species will be difficult or impossible.

A specific RF level and compensation voltage will permit only aparticular species of ion (according to mobility) to pass through thefilter to the detector. By noting the RF level and compensation voltageand the corresponding detected signal, various ion species can beidentified, as well as their relative concentrations (as seen in thepeak characteristics).

Consider a plot of mobility dependence on electric field, as shown inFIG. 1C. This figure mobility versus electric field strength for threeexamples of ions, with field dependent mobility (expressed as thecoefficient of high field mobility, a) shown for species at greater,equal to and less than zero. The velocity of an ion can be measured inan electric field, E, low enough so that velocity, V, is proportional tothe electrical field as V=KE through a coefficient, K, called thecoefficient of mobility. K can be shown to be theoretically related tothe ion species and gas molecular interaction properties. Thiscoefficient of mobility is considered to be a unique parameter thatenables the identification of different ion species and is determinedby, ion properties such as charge, size, and mass as well as thecollision frequency and energy obtained by ions between collisions.

When the ratio of E/N is small, K is constant in value, but atincreasing E/N values, the coefficient of mobility begins to vary. Theeffect of the electric field can be expressed approximately asK(E)=K(0)[1+α(E)]where K(0) is a low voltage coefficient of mobility, and α is a specificparameter showing the electric field dependence of mobility for aspecific ion.

Thus, as exhibited in FIG. 1C, at relatively low electric fieldstrengths, of say less than approximately 8,000 volts per centimeter(V/cm), multiple ions may have the same mobility. However, as theelectric field strengths increase, the different species diverge intheir response such that their mobility varies as a function of theapplied electric field. This is a clear expression of the fact that ionmobility is independent of applied electric field at relatively lowfield strengths but is field-dependent at higher applied fieldstrengths.

FIG. 1B demonstrates that each species can have a unique behavior inhigh fields according to its mobility characteristics. The ions passingthrough the filter are detected downstream. The detection signalintensity can be plotted, resulting in display of a characteristicdetection peak for a given RF and Vcomp. Peak intensity, location, andshape are typically used for species identification.

However, a problem occurs, especially with FAIMS devices, in thatrelatively complex samples can be very difficult to discriminate. Firstof all, the peaks as seen in the typical FAIMS spectra are generallybroad in width. Therefore, compounds having similar peak compensationvoltages may be difficult to separate from one another. Indeed, theremay be particular conditions where two different chemicals actuallyexhibit the same peak at the same compensation voltage at a givenasymmetric RF field.

For example in FIG. 1D, there are four compounds each with a uniquecharacteristic mobility curve that expresses the mobility dependenceassociated with that compound at each of various peak RF values andcompensation voltage levels. Four different chemical compounds areshown, including lutidine, cyclohexane, benzene, and a chemical agentsimulant dimethyl-methyl-phosphonate (DMMP). Each curve shows detectionpeaks at the various field conditions that in total are characteristicfor the compound. As shown, there is a region 100 in which the mobilitycurves for DMMP and cyclohexane overlap with one another. Therefore,operating in a peak RF voltage region of from approximately 2,500 to2,650 volts, at around −6 to −8 volts compensation, one would find itimpossible to discriminate between the two compounds upon a single scan.In other words, the conventional spectral scan would plot theoverlapping peaks as a single peak at that field condition.

A cylindrical FAIMS device is described in U.S. Pat. No. 5,420,424,where the amplitude of the asymmetric periodic potential is in the rangeof about 1 to 6 Kv or 2 to 5 Kv, and preferably at about 3 Kv, dependingon the ionic species of interest. After the magnitude of the asymmetricvoltage has been set, the compensation voltage is held constant orscanned to provide separation of the ionic species.

Even with these improvements, ion species detection is not error free,especially with complex sample mixtures. False negatives are dangerous,and false positives can be expensive and reduce trust in the device.This can be very serious where harmful compounds are being monitored. Itis also desirable to have a fast and simple apparatus to achieve suchdetections with improved accuracy.

SUMMARY OF THE INVENTION

The present invention is directed to a method and system foridentification of unknown species of ions traveling through anasymmetric excitation field, the identification being based on the knowncharacteristic mobility behavior of ion species under known fieldconditions.

Illustrative apparatus of the invention includes an ionization section,a filter section, a detection section, an identification section, and acontroller section. The controller (e.g., microprocessor, laptop, etc.)may typically incorporate the identification section (lookup table,comparator, etc.).

In practice of the invention, we disclose innovations for isolating ionspecies of interest in a sample and positively identifying the specieswith a high degree of reliability. We apply techniques for improving thedetection and identification processes. This process may also includeseparating the ions from background noise or from other ion species inthe sample.

In one significant aspect, the present invention intentionally controlsand uses changes of the filter field (i.e., changes in “fieldconditions”) for better revealing and isolating ion species in thesample. The ionization and filter sections may assume many differentphysical forms.

As ions are passed through the filter, they deposit charges at adetector. The intensity of the detection is then recorded against thecompensation voltage (Vcomp) for a set RF condition (Vrf). Spectralpeaks may also be determined while Vcomp is scanned through a range.

The present invention then takes this process further. Specifically, wehave identified stratagem for improving species discrimination byintentionally controlling field conditions in a manner that results inimproved isolation of ion species. In one embodiment, this involvesdetecting ion species behavior in response to at least two differentapplied RF field strengths, and thus at two different sets of fieldconditions. At each ion species detection we associate the appliedcompensation and RF with the detection signal and match or correlatethis with known data to identify the detected ion species.

Several methods of adjusting field conditions may be used, includingadjusting field strength, frequency, aspects of the waveform asymmetry,pulse shape, duty cycle, and the like, to effect meaningful changes infield conditions that affect ion mobility. These alternatives areselected for the ability they provide in separating and isolating ionspecies in the sample. This assumes that the ion species are sensitiveto such changes. As long as there is a desirable effect on the mobilitybehavior of the ions in the field then we can make use of this control.In all events these controls are directed to causing one species tobehave differently from another species in the field so that a morerefined or better defined set of ions can be passed to the detector.

Therefore, for purposes of this invention, we define “field conditions”and “set of field conditions” as any combination of compensation and RFestablished in the gap between the filter electrodes as may affect ionmobility. Field conditions are considered to be different whenattributes of the RF or compensation have been changed, whether thistakes the form of adjustment in frequency, intensity, asymmetry,periodicity, pulse shape or similar variables. Nevertheless, we cancontrol the field conditions and the energy in the field in a mannerthat has differential effect upon ion mobility in the field. We use thisdifferential effect in controlling ion filtering. In a preferredembodiment, “field conditions” also will be understood to take intoaccount various other aspects such as temperature, flow rate, pressure,and flow volume in the filter, as well as the nature of the carrier gas,if any.

Field conditions can be controlled by several techniques in practice ofthe invention. For example, frequency has an effect on the ‘selectivity’(width) of the output scanned peaks. This can be implemented by changingthe value of a fixed operating frequency or by dynamic frequencymodulation where a range of frequencies could be scanned, for example.Control of pulse shape, i.e., square, triangular, sinusoidal, ramp, alsomay be adjusted, where shape may be used to affect response of the ionin the field in a known manner. Magnetic fields may also be used tocontrol flow of ions according to known response characteristics.

The compensation voltage Vcomp may be a separate DC voltage or it may beimposed on the RF signal Vrf, such as by varying the duty cycle. Theterm compensation therefore will be understood as an adjustment to thefield by bias voltage or other means that enables tuning the field topass a desired species of ion to the detector. When we run a spectralscan, we normally scan the compensation voltage through a range ofvalues. However, varying the duty cycle or pulse width can have aneffect similar to adjusting or scanning the compensation voltage. Thelatter can be accomplished by holding the pulse width constant whilevarying the frequency or by holding the frequency constant while varyingthe pulse width. We also can apply techniques of pulse amplitudemodulation, which is yet another method for generating and adjusting thecompensation. Alternatively, with a fixed pulse amplitude, compensationcan be generated by varying baseline voltage. These controls can beproduced with analog circuitry or can be generated digitally. These andstill other control strategies are within the spirit and scope of theinvention as will appear to a person skilled in the art.

We therefore exercise our ability to control ion behavior in theelectric field by control of field conditions, knowing that differention species will pass through the filter depending upon these fieldconditions. In one example, we set the field strength, e.g., amplitudeof the RF signal, and then adjust or shift the compensation to a levelneeded to detect an ion species. If we detect a peak at this set offield conditions, we take this detection data (noting detection peak andfield conditions), and then compare this to a store of mobility behaviorof known ion species. Upon finding a match or near match, we can make areliable identification of the species of the detected ions.

We further exercise field control to distinguish between multipledetection data that may require further clarity. Thus at one set offield conditions some peaks may seem to overlap, but after making afield adjustment such as changing field strength or compensation, theseoverlapping peaks will be separated and be separately processable aswill enable separate identification of the species each represents.Detections thus proceed where detection data and field conditions arecorrelated with stored data to make positive species identifications.

It will be appreciated by a person skilled in the art that a “reactantion peak” (RIP) may be detected in a FAIMS device and will be associatedwith ions that result from ionization of the background environment inthe drift tube. This background may include molecules of carrier gasthat are ionized, and perhaps also water molecules that becomeprotonated, during the ionization process. Peaks associated withdetection of these ions are referred to as “reactant ion peaks” asopposed to peaks associated with detection of chemical ions of interest.

In practice of the present invention, in one example, increasing the RFfield strength typically has a much more dramatic effect on thebackground RIP than on a sample ion species; as a result of sampling attwo or more of a series of different field conditions (whether thedifference is in the RF field or the compensation), the RIP peak can beshifted away from the peak for an ion species of interest.

This separation of detection data isolates the ion species of interestfrom the background detection data and results in a cleaner and moreaccurate species detection and identification. In this manner, detectionaccuracy is improved and false positives are reduced in practice of theinvention.

Furthermore, intentionally changing or scanning across a range of fieldconditions can cause the peaks associated with complex or clusteredcompounds to shift away from peaks associated with monomers in a sample.This enable better species isolation. Furthermore, with sufficientincrease in field strength, clustered compounds will even tend todecluster and resolve into identifiable constituents. Therefore, asingle complex compound may be identified by its characteristiccomponent ions or sub-clusters, again based on comparison of fieldconditions and detection data compared to a known data store.

In embodiments of the invention, we control ionization, such as byincreasing ionization energy and fragmenting the sample intocharacteristic component parts. This increases specificity of thedetection data. In other embodiments, we increase the RF energy in thefilter section to accomplish fragmentation. This again enables componentparts of a sample to be separately detected, the combination ofdetections enabling us to more accurately identify the ion species inthe sample. Thus we can control actions in the ionization section or inthe filter section to favorably impact the quality of the detectionsignal.

In the detector region, we note the field conditions in the filtersection (as well as ionization and flow) and then we correlate this withdetection intensity data. This characterizes an ion species detection ofunknown type. This detection data is compared to stored detector datafor known species at known filed conditions and a detectionidentification is made. This approach is simplified, but may be adequatefor various embodiments of the invention.

However, in practice of further embodiments of the invention, we also dofurther processing of the detection signal using techniques such as byevaluating peak spectral energy, generating mobility curves, curvematching, and the like. This enables a more definitive detectionprocess.

In one practice of the invention, a detection is made of an ion speciesat at least two field conditions. Identification is made by collectingmultiple detection data representing a signature of the detected ionspecies in these field conditions, and then by comparing this signaturedata to a store of known species signatures. The ion species to beidentified may be traveling alone or in a group of ions of same ordiffering characteristic mobility behavior. Nevertheless, we can achievespecies-specific isolation and identification.

In yet another embodiment, a FAIMS device operates simultaneously inboth positive ion detection mode (“positive mode” or “positive ionmode”) and negative ion detection mode (“negative mode” or “negative ionmode”) for complete real-time sample analysis. Alternatively, twoseparate FAIMS devices may operate in tandem, one in each mode, anddetection results can be processed either seriatim or simultaneously andcombined for complete real-time sample analysis.

A preferred method and apparatus detects multiple species simultaneouslybased on both ion mobility and ion polarity. A preferred method andapparatus of the invention includes a FAIMS spectrometer applied tofiltering and simultaneous transport and detection of positive andnegative ion species from a sample including mercaptans and othersulfur-containing compounds, and air, methane or other gases.

In one practice of the invention, a compensated asymmetric high RF fieldis used to separate sulfur-containing compounds (such as mercaptans)from a hydrocarbon background (such as methane). The sample is ionizedand the ions representing sulfur-containing compounds (such asmercaptans) are detected according to polarity (i.e., for the most partas negative ions). The hydrocarbons are detected according to polarity(i.e., for the most part as positive ions) in the same device. Thesedetections may even be performed simultaneously where dual detectors areoppositely biased.

In one specific end use, the invention enables detection of traceamounts (ppm, ppb, ppt) of mercaptan in varying and even highhydrocarbon backgrounds. The device is also able to characterize thehydrocarbon gas backgrounds. A preferred practice of the invention hasthe ability to detect trace amounts of sulfur-containing compounds(e.g., mercaptans) in varying and even high hydrocarbon backgrounds andto characterized the hydrocarbon backgrounds in the same devicesimultaneously.

In this embodiment of the invention, a gas sample havingsulfur-containing compounds (e.g., mercaptans) and methane (or othergases including air) are ionized and flowed through a FAIMS filter.Negative ions are detected indicative of the concentration and identityof the sulfur-containing compounds. The same test is run again andpositive ions are detected indicative of the hydrocarbon gas in thesample.

These compounds are passed by the FAIMS filter based on their mobilitybehavior and their having similar trajectories in the presence ofcompensated electric filter fields. The passed ions are then furtherseparated based on polarity, wherein, for example, mercaptans can bedistinguished from a gas such as air or methane. In the negative mode,mercaptans are detected and in the positive mode, the gas (e.g.,methane) is distinguished from the mercaptans. Both modes can be runsimultaneously.

It will thus be appreciated that it has been found generally thatsamples such as hydrocarbon gas will separate into predominantlypositive ion species and sulfur-containing compounds (e.g., mercaptans)will separate into predominantly negative ion species. The preferredFAIMS spectrometer is a simple and low cost device, which can performsubstantive quantitative analysis of complex mixtures havingsulfur-containing compounds (e.g., mercaptans) in a gas, such ashydrocarbon or air.

In practice of the invention, a single positively biased detectorelectrode downstream from the filter will detect the negatively chargedion stream (negative mode). A single negatively biased detectorelectrode downstream from the filter will detect the positively chargedion stream (positive mode). A detection signal is generated as theseions deposit their charges on a detector electrode. These detections canbe correlated with the RF signal, compensation voltage and detectorbias, to identify the detected ion species.

Where two detector electrodes are provided downstream, each oppositelybiased, both positive and negatively charged ion species can be detectedand identified. In one practice of the invention, where mercaptans weredetected in hydrocarbon background, the asymmetric voltage applied tothe ion filter electrodes ranged from about 900 to about 1.5 kV (highfield condition), and a low voltage of about −400 to −500 V (low fieldcondition). The frequency ranged 1–2 MHz and the high frequency had anapproximate 30% duty cycle, although other operating ranges arepossible. In one embodiment, the detector electrodes were biased at +5vand −5v. Now the mercaptans are detected in the negative mode and thehydrocarbon gases can be detected in the positive mode.

The above identification process, while remarkably powerful and useful,may in some applications be substantially improved and simplified byincorporation and use of α parameter (coefficient of high fieldmobility) information and α curves as part of positive, highly reliable,identification process using unique mobility signatures.

Furthermore, we have found that the field-dependent mobility of aspecies can be expressed as an α function. In point of fact, thecoefficient of field-dependent mobility, α, for a species is expressedas a function of the electric field. The resulting curve showing theexperienced mobility or “α” curve, is a unique signature for thatspecies. Furthermore, this signature can be expressed in adevice-independent function.

The characteristic mobility for each species can be plotted at multiplefield conditions (i.e., detection intensity noted at a series of fieldconditions), and this and can be expressed as a unique “α function” thatidentifies the ion species uniquely.

We note that use of the field mobility dependence coefficient α for asingle set of field conditions does not necessarily result in a uniqueidentification, because multiple different species can happen to havethe same mobility in that single set of field conditions. We have foundhowever that obtaining multiple a data sets for a detected speciesenables us to uniquely identify that species by its computed “α curve”even when it is indistinguishable from other species in one set of fieldconditions.

In one practice of the invention, we use the α function to make uniqueidentification of a specific ion species in a sample by using twoclosely related detection data sets (i.e., noting detection intensity attwo different but close sets of field conditions). We use these relatedsets of field condition values as two points on a curve, and from whichwe generate the slope and sign of the curve. We then can associate signand slope with each detection and can compare to stored known detectionresults. Thus we can identify a detected ion species (with twodetections) according to its associated mobility curve. Furthermore, wehave determined that this mobility curve is species specific, and wehave further identified a process for making such identificationdevice-independent. In any case, we compare detected and computed datato a store of known data to make positive identification of the speciesof detected ions.

The system of the present invention (which may be expressed as eithermethod and/or apparatus) is for identification of species of unknownions that travel through a varying excitation field. The field ischaracterized as having varying influence upon the mobility behavior ofthe species (single or plural) of ions (single or plural) travelingthrough the field. The identification of the detected ion(s) is based oncorrelating the field-dependent mobility behavior of the detected ion(s)to a store of known field-dependent mobility behavior(s) of at least oneknown species.

We can scan at multiple field conditions to obtain multiple detectionpeaks. We can also fragment, decluster, or use dopants to control orgenerate additional or clarify existing detection peaks as needed. Wecan use these alternative to generate multiple detection data for aparticular situation, and this data is processed using variousevaluation strategies, such as curve/peak matching, etc., and then we doa lookup comparison for positive identification of the species of thedetected ion(s). A match enables positive identification of a detectedion species in a sample.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, features and advantages of theinvention will be apparent from the following more particulardescription of preferred embodiments of the invention, as illustrated inthe accompanying drawings in which like reference characters refer tothe same parts throughout the different views. The drawings are notnecessarily to scale, emphasis instead being placed upon illustratingthe principles of the invention.

FIG. 1A illustrates an asymmetric field having a peak RF, time period,and duty cycle.

FIGS. 1B-1 and 1B-2 are a typical display of detected abundance versusapplied compensation voltage for a given field strength in a fieldasymmetric ion mobility spectrometer, first for acetone alone and secondfor a combination of o-xylene and acetone (Prior Art).

FIG. 1C is a plot of mobility dependence upon electric field strengthfor three different compounds (Prior Art).

FIG. 1D is a plot showing peak detections across a range of combinationsof peak Radio Frequency (RF) voltage and compensation voltage for fourdifferent compounds (Prior Art).

FIG. 2 is a schematic of a preferred field asymmetric ion mobilityspectrometer in practice of the present invention.

FIGS. 3A and 3B illustrate positive and negative mode spectra fordifferent amounts of ethyl mercaptan in practice of the presentinvention.

FIGS. 3C through 3G illustrate the affect of changes in fieldconditions, such as changes in compensation, on specific spectra, andshowing divergent behavior of monomer and reactant ion peak (RIP)detections with changes in field for detecting sulfur hexafluoride (SF6)in practice of the invention.

FIGS. 4A and 4B illustrate changes in peak location change incompensation in practice of the present invention.

FIGS. 5A and 5B illustrate ability to discriminate between detected ionspecies by changes in field conditions in practice of the presentinvention.

FIGS. 6A and 6B illustrate the affect of changes in field conditions,such as changes in compensation, on specific spectra, and showingdivergent behavior of monomer, cluster, and reactant ion peak (RIP)detections with changes in field for hexanone and octanone in practiceof the present invention.

FIG. 7 illustrates effect of changes in field conditions on location ofindividual detection peaks and ability to separate peaks in practice ofthe present invention.

FIGS. 8A and 8B respectively show a plot of compensation versus fieldstrength for detected monomer and cluster ion peaks for a family ofketones in practice of the present invention.

FIG. 8C includes Table 1, which is a collection of detection data fromwhich the curves of FIGS. 8A and 8B were generated for a group ofmonomer and dimers (clusters) for eight ketones in practice of thepresent invention.

FIGS. 9A and 9B illustrate the results of calculating normalized alphaparameter curves in practice of the present invention.

FIG. 10A shows a sequence of steps of a computer process used to acquiredata concerning a particular chemical ion species in practice of thepresent invention.

FIG. 10B shows a diagram of one possible data structure for a library ofstored compound data measurement information in practice of the presentinvention.

FIG. 10C is a series of steps that may be applied to perform a chemicalrecognition in practice of the present invention.

FIG. 10D is a series of steps that may be added to the data acquisitionand chemical recognition processes using alpha curve fitting in practiceof the present invention.

FIG. 10E is a diagram of a more complex data structure that can be usedin practice of the present invention.

FIG. 10F is a sequence of processes that may be used to distinguishmonomer and cluster peak responses in practice of the present invention.

FIG. 10G is a diagram of a process showing how monomer and clusterscores may be combined in practice of the present invention.

FIG. 11A, 11B show spectra before and after processing according to alow-field enhanced DMS embodiment of the invention.

FIG. 12A, 12B show DMS-IMS embodiments of the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

A. A Field Asymmetric Ion Mobility Spectrometer

By way of general introduction, the present invention has particularapplication to high field ion mobility spectrometry and includes therecognition that improved identification or discrimination of compoundsmay be achieved. However, the invention may be practiced in manydifferent field-driven and gas-driven embodiments.

One aspect of our innovation can be stated in terms of the steps of aprocess. Specifically, a system is used to cause species of unknown ionsto travel through an excitation field. The field has a varying influenceupon the behavior of different ions as they travel through the field.Identification is based on this known field-dependent behavior ofdifferent species of ions. Identification of the species may occur bycomparison of results observed under one set of field conditions withresults observed under another set of field conditions.

Various techniques may also be applied to increase the amount of, orconfidence in, the detection data and subsequent identifications. Theresult is more accurate species detection with reduced false positives.

Now more particularly, one device that may make use of the invention,shown in FIG. 2, is a field asymmetric ion mobility spectrometer (FAIMSalso referred to as a DMS) apparatus 10. The apparatus accommodates theflow of a carrier gas G which carries sample S from sample inlet 12 atone end of the flow channel 11 to a sample outlet 13 at the other end ofthe flow channel.

In operation, the sample is drawn from the environment or received froma front end device, such as a gas chromatograph, and flows into anionization region 14. Compounds in the sample are ionized by anionization source 16 as the sample flows through the ionization region14, creating a set of ionized molecules 17+, 17−, with some neutralmolecules 17 n, of various chemical species that are in the sample S.This may include monomer ions and cluster ions. Such clusters may becreated when a monomer combines with water molecules or other backgroundmolecules, and the combination is ionized.

The carrier gas carries the ionized sample into the ion filter region 18in between filter electrodes 20, 22 of ion filter 24. Filtering proceedsnow based on differences in ion mobility in the filter field, which isinfluenced by ion size, shape, mass and charge.

More specifically, an asymmetric field applied across the filterelectrodes alternates between high and low field strength conditions infilter region 18. The ions move in response to the field, based on theirmobility characteristics. Typically the mobility in the high fieldcondition differs from that of the low field condition. This mobilitydifference produces a net transverse displacement of the ions as theytravel longitudinally through the filter 24, defining an ion trajectory.

In one example, the carrier gas (or other flow mechanism) carries theionized sample into the ion filter region between the filter electrodes.Filtering proceeds based upon differences in ion mobility, which isinfluenced by the ion size, shape, mass, and charge. This enablesdiscrimination of ions species based upon their mobilitycharacteristics.

In accordance with the preferred embodiment of the present invention, anasymmetric field voltage or dispersion voltage, variously referred toherein as “RF”, “Vrf”, or “Vdisp”, is applied across the filterelectrodes as an RF voltage driven between high and low field strengthconditions. This excursion causes the ions to move transverse to theflow as they flow through the flow channel, with the transverse motionbeing representative of their characteristic ion mobility. Typically,the mobility in the high field condition differs from that of the lowfield condition. This mobility difference produces a net transversedisplacement of the ions as they travel longitudinally through thefilter between the electrodes.

The compensation voltage, Vcomp, causes a particular ion species to bereturned toward the center of the flow path, thus being able to exit thefilter without colliding with the filter electrodes and without beingneutralized. Other species will not be sufficiently compensated and willcollide with the filter electrodes 20, 22 and will be neutralized. Theneutralized ions are purged by the carrier gas, or by heating the flowpath 11, for example.

B. FAIMS Device Detecting Response Under Several Field Conditions

Therefore, in the presence of set asymmetric field conditions, asapplied through Vrf and Vcomp, discrimination of ions from each otheraccording to mobility differences can be achieved. However, in a singlemobility scan, when two ions are compensated by the same compensationsignal in a given RF field, there is, in general, no way to discriminatebetween them after they pass through the filer 24. This would happenwhere they exhibit the same mobility characteristics for those givenfield conditions.

In practice of an embodiment of the present invention, however, theseions can be discriminated if they have different polarities, as such isthe example with ions 17− and 17+. Thus the device of FIG. 2 can beoperated to simultaneously detect both positive and negative ions in thegas flow, enabling identification of two compounds simultaneously orenabling detection of two modes of a single compound simultaneously.

More specifically, the two species of ions 17+ and 17−, enter thedetection region 25 where further separation occurs followed by theirintensity determination. In a preferred embodiment, the detector 26includes a first detector electrode 28 and a second detector electrode30. Electrode 28 may be positively biased and therefore attracts ion 17−and repels ion 17+. Electrode 30 may be biased negatively, and attractsions 17+ while repelling ions 17−. Thus, this final stage of separationresults in the separated ions depositing their charges on theappropriately biased detector electrodes 28 or 30. The signals generatedby the ions collecting at detector electrodes 28 and 30 are amplified byrespective amplifiers 36 and 38 to provide signals to command andcontrol unit 34.

In the preferred embodiment, the invention applies to high fieldasymmetric waveform ion mobility spectrometry in a device configurationsuch that the flow channel 18, filter electrodes 24, and detectorelectrodes 28 are all provided, preferably in a compact package. Thisprovides for the ability to produce a compact, low cost device which mayhave incorporated upon a common substrate the various system componentsand possibly support electronics. Spectrometers according to the presentinvention may therefore be manufactured using well known microchipmanufacturing techniques while at the same time providing highlyeffective analytical equipment for use both in the field and inlaboratory environments.

It is a feature of a FAIMS spectrometer that by application ofcompensation to the filter field, ions having specific mobilitycharacteristics will be returned toward the center of the flow path andwill pass through the filter. Therefore, in practice of the invention,discrimination of ions from each other according to the compensationresults in a ions having a particular mobility passing to detector 26(which may be an on-board electrode arrangement or may include anoff-board detector such as a mass spectrometer, for example). All otherspecies will not be sufficiently compensated and will collide with thefilter electrodes and will be neutralized.

In the preferred embodiment, the invention applies to high fieldasymmetric waveform ion mobility spectrometry in a device configurationsuch that the flow channel 18, filter electrodes 24, and detectorelectrodes 28 are all provided in a compact package. This provides forthe ability to produce a compact, low cost device which may haveincorporated upon a common substrate the various system components andpossibly control electronics 40. Spectrometers according to the presentinvention may therefore be manufactured using well known microchipmanufacturing techniques while at the same time providing a highlyeffective analytical equipment for use both in the field and inlaboratory environments.

The control unit 40 contains a number of electronic devices that performa number of important functions in accordance with the presentinvention.

These include RF voltage generator 42, compensation voltage generator44, a microprocessor unit (MPU) 46, memory 47, an analog-to-digitalconverter 48, and display 49. The microprocessor 46 provides digitalcontrol signals to the RF (AKA “dispersion”) voltage generator 42 andcompensation voltage generator 44 to generate the desired drive voltagesfor the filter 24, respectively. They may include, for example,digital-to-analog converters that are not shown in detail.

The microprocessor 46 also coordinates the application of specificdispersion voltages Vrf and compensation voltages Vcomp with observedresponses from the detector 26, as read through the analog-to-digitalconverters 48. By comparing an observed response of, for example, peakobserved abundance of a particular ion across a range of compensationvoltages, Vcomp, the microprocessor 46 can identify particular compoundssuch as by comparing particular response curves against a library ofresponse curves or other data stored in its memory 47. The results ofthe comparison operation can then be provided in a form of anappropriate output device such as a display 49, or may be provided byelectrical signals through an interface 50 to other computer equipment.

One detailed example of how the microprocessor 46 can detect responsesunder multiple field conditions is described below in connection withFIGS. 10A–10G.

In practice of an embodiment of the invention, a range of applied peakRF voltages may run from less than 1,000 V/cm to 30,000 V/cm, or higher.The frequency ranges may run from 1 to 20 Megahertz (MHz), with thehighest frequencies having an approximately 30 percent duty cycle,although other operating ranges, voltages, field strengths, duty cycles,wavelengths and frequencies are possible in embodiments of the presentinvention.

In practice of one embodiment of the invention, the processor 46 scansor sweeps a range of compensation voltages (i.e., a scan) for aparticular RF field strength as controlled by the applied peak RF(dispersion) voltage for a first measurement set, and then the RF isreset to another level and the compensation voltage is scanned again toestablish a second measurement set. This information is correlated withdetection signals obtained as set forth above, and compared to look uptables, a compound identification is able to be made.

More generally stated, an object of identification is to detect theintensity of the ions passing though the filter and to associate thisintensity with field conditions. Each identified compound is to beassociated with at least one particular spectral peak and then we canuse the process of peak evaluation or peak matching to identifycompounds, peak by peak. This process is not limited to single peaks andmultiple peaks detected in a single scan also can be used to define asignature for the responsible particular combination of compounds. If itis a recurring phenomenon, then such complex signature can be part ofour table of look up data.

If a particular combination of peaks in a spectral scan is known andimportant, data representing these multiple peaks can be stored andfuture detection data can be compared against this stored data. Forexample, under controls field conditions, such as at raised fieldstrengths, a clustered compound may become declustered. The resultingdetection results in a signature of peaks that can be used to identifythe source compound being detected even in as detected in a single scan.

In practice of the invention, we have developed an ion mobility-basedmethod and apparatus for detection of sulfur-containing compounds in ahydrocarbon background. In one example, detection and measurement ofnegative ions is done in a negative mode, and detection and measurementof positive ions is done in a positive mode. The detected data enables aquantitative measurement of concentration of these sulfur-containingcompounds, independent of the hydrocarbon background.

C. Positive and Negative Field Measurement

Referring to the illustrative embodiment of FIG. 2, a single positivelybiased detector electrode 30 (or 28) downstream from the filter can beused to detect the negatively charged ion stream (negative mode), andoptionally another other electrode 28 (or 30) may be negatively biasedto deflect the negative ions to the positively biased detectorelectrode. Also, a single negatively biased detector electrode 28 (or30) downstream from the filter can also detect the positively chargedion stream (positive mode), and optionally the other electrode 30 (or28) may be positively biased to deflect the positive ions to thenegatively biased detector electrode.

Thus, positive and negative modes may be detected in the FAIMSspectrometer, seriatim or in parallel devices. Optionally, in a singlescan of a single device, we are able to demonstrate simultaneouscollection of multiple data by detecting both modes simultaneously.Referring again to the illustrative embodiment of FIG. 2, in oneexample, a single positively biased electrode 30 downstream from thefilter is used to detect the negatively charged ion stream (negativemode); meanwhile electrode 28 is negatively biased to deflect thenegative ions to this positively biased detector electrode 30 so as toimprove collection efficiency. However, simultaneously, if desired, thenegatively biased electrode 28 detects the positively charged ion stream(positive mode) that is deflected by the positively charged electrode30.

A detection signal is generated as these ions deposit their charges on arespective detector electrode. These detections can be correlated withthe RF signal, compensation voltage and detector bias, to definitivelyidentify the detected ion species. Thus Where two detector electrodesare provided downstream, each oppositely biased, both positive andnegatively charged ion species can be detected and identifiedsimultaneously.

In one embodiment, the present invention was used for detection of traceamounts (ppm, ppb, ppt) of mercaptan in varying and even highhydrocarbon backgrounds. The device is also able to characterizehydrocarbon gas backgrounds. For example, the present invention iscapable of detecting mercaptans, such as ethyl mercaptan in a methanebackground, and is also capable of detecting a gas, such as methane, ina mercaptan background.

In this practice of the invention, where mercaptans were detected inhydrocarbon background, the asymmetric voltage applied to the ion filterelectrodes ranged from about 900 to about 1.5 kV (high field condition),and a low voltage of about −400 to −500 V (low field condition). Thefrequency ranged 1–2 MHz and the high frequency had an approximate 30%duty cycle, although other operating ranges are possible. In oneembodiment, the detector electrodes were biased at +5v and −5v. Now themercaptans are detected in the negative mode and the hydrocarbon gasescan be detected in the positive mode.

The hardware used to drive the system my be conventional. For example,amplifiers, such as Analog Devices model 459 amplifier, may be used. Thesignal may be processed in a conventional manner, such as with aNational Instruments board (model 6024E) to digitize and store the scansand with software to display the results as spectra, topographic plotsor graphs of ion intensity versus time. The ionization source may be aplasma or radioactive source or a UV lamp, or the like.

The present invention recognizes that ions that pass through the filterdefine a mobility species 17 m. In a further example, this species canbe further separated by polarity, such as by correct biasing of thedetector electrode pair 28, 30. An example is shown in FIG. 2 where thespecies defined by ions 17+, 17− passes through filter 24. This speciescan be further separated to positive and negative species or sub-speciesby holding one electrode, e.g., detector electrode 28, at one polarity,say negative, and another electrode, e.g., detector electrode 30, at apositive bias. Now ions 17+ will be attracted to electrode 28 and willbe detected and ions 17− will be attracted to and will be detected atelectrode 30.

Therefore, apparatus of the invention can be operated to simultaneouslydetect both positive and negative ions in a species flowed from thefilter. This enables identification of multiple compounds simultaneouslyin practice of the innovation.

More specifically, the apparatus 10 discriminates between ions andneutrals based on their mobility behavior, resultant trajectory andpolarity. Therefore only ion species 17− and 17+ with a particularmobility behavior and resultant trajectory in the presence of a givencompensation bias will be passed by the filter, for a given asymmetricRF field condition.

It will be appreciated by a person skilled in the art that thiscompensation bias must be established for the compounds being tested.The apparatus of the invention is very stable and test results arerepeatable. Therefore, in a preferred practice of the invention,creation of a history table for species of ions detected, correlatedwith compensation voltage and RF field, enables continuous use of thedevice without the need for further calibration. However, it is alsowithin the scope of the invention to calibrate the system using thereactant ion peak or a dopant peak, for example.

In one practice of the invention, a mobility species 17 m was passed byfilter 24. That species included hydrogen sulfide ions 17 m− and methaneions 17 m+, both of which have a similar resultant trajectory, for givencompensated asymmetric field. Other positive and negative ions areneutralized given their different and unselected mobilitycharacteristics. (Neutralized ions 17 n are purged by the carrier gas orby heating the flow path 11, for example.)

The two species of ions 17 m+ and 17 m− have entered into the detectionregion 25, where further species separation occurs, followed bydetection. In a preferred embodiment, detector electrode 28 is biasedpositive and therefore attracts hydrogen sulfide species 17 m− whilerepelling methane species 17 m+. Electrode 30 is biased negative andattracts methane species 17 m+, while deflecting sulfide ions 17 m−.Thus this final stage of separation results in the separated ionsdepositing their charges on the appropriately biased detector electrodes(i.e., negative charge on positive electrode and positive charge onnegative electrode).

The asymmetric field and compensation bias are generally applied tofilter electrodes 20, 22 by drive circuits 32 within command and controlunit 34. The signals generated by the ions at the detector electrodes28, 30 are amplified by amplifiers 36, 38, also under direction andcontrol of unit 34 (communicating by wires, ribbon cable, or the like).A computer (or microprocessor) including a data store, generally shownat 40 correlates historical data for the device with the drive signalsapplied to the filter electrodes and with detection signals fromamplifiers 36, 38, and presents a compound identification information toa readout device 49. In this example, an indication of the amount ofhydrogen sulfide and of methane detected would be indicated.

In a particular embodiment, the command and control unit 34 alsocoordinates ion flow and the application of specific dispersion voltagesVrf and compensation voltages Vcomp with observed responses from thedetector 26. By comparing an observed response of, for example, peakobserved abundance of a particular ion across a range of peak RFvoltages, Vcomp, the microprocessor can identify particular compoundssuch as by comparing particular response curves against a library ofresponse curves stored in its memory. The results of the comparisonoperation can then be provided in a form of an appropriate output devicesuch as at a display, or may be provided by electrical signals throughan interface to other computer equipment.

In this embodiment of the invention, a single spectrometer device 10provides a detector with dual detector electrodes 28, 30. One electrodemay be positively biased and the other negatively. In the positive mode,the negatively biased detector electrode acts for ions of the samepolarity as a deflector electrode, deflecting those ions toward thepositively charged detector electrode for detection. In the negativemode, the one detector electrode that is positively biased acts for ionsof the same polarity as a deflector electrode, deflecting those ionstoward the negatively charged detector electrode for detection. Insimultaneous operation, each of these detector electrodes has a dualrole, acting as both a deflector electrode and detector electrode, forrespectively charged ions.

In practice of one embodiment of the invention, by sweeping thecompensation bias over a predetermined voltage range, a completespectrum for sample S can be achieved. By intelligent control of thesystem command and control unit 40 it is possible to select specificfield conditions and as a result it is possible to allow ion species ofinterest to pass through the filter while all other candidates areneutralized. In another embodiment, the compensation bias is in the formof varying the duty cycle of the asymmetric field, without the need forcompensating bias voltage. In any such manner, the apparatus is tunable,i.e., it can be tuned to pass only desired selected mobility species,which can be further clarified with the above polarity mode detections.

In a preferred embodiment of the invention, the high voltage RF signalis applied to one filter electrode, e.g., electrode 20, and the otherelectrode, e.g., electrode 22, is tied to ground. A compensation voltageis then applied to one or across the filter electrodes according to theions species to be passed. It has been further found that biasing thedetector electrodes 28, 30, with a floating bias, such as with electrode28 being held at −5 volts and electrode 30 being held at +5 volts, leadsto good performance for detection of mercaptans in hydrocarbon or airbackgrounds.

Experimental data verifies viability of this approach. Turning now toFIGS. 3A and 3B, we show detection of ethyl mercaptan independent ofvarying background gas level. FIG. 3A shows positive ion detection mode(“positive mode”) detection, where a detector electrode is negativelybiased and attracts positive methane ions 17 m+ for detection. FIG. 3Bshows the effect of varying methane concentration on ethyl mercaptanspectra in the negative ion mode (“negative mode”). Here a detectorelectrode is positively biased and attracts the negative mercaptan ions17 m− for detection.

These spectra are for different amounts of ethyl mercaptan in an air andmethane drift gas mixture in positive mode operation and then innegative mode operation of an embodiment of the invention. The mercaptansignatures are clearly captured independent of the air-hydrocarbon driftgas background, at various dosage levels. The detected sample peaks arefully isolated from the background. In FIG. 3A the reactant ion peak(RIP) is clearly isolated; and in FIG. 3B the background is flat.

The foregoing is an example of ionization of a particular compound(s)that results in a combination of positive and negative ions. Both iontypes can be evaluated simultaneously in practice of an embodiment ofthe invention for unambiguous identification of the test chemical. Forexample, a mercaptan sample when ionized may have predominantly negativeions, but may also include positive ions. Now identification can be moreaccurate and false positives reduced by using both modes simultaneouslyto state a unique detection signature. Specifically, while the negativemode fairly identifies the mercaptan, the added positive ion identifierrelated to mercaptan enables identification in a complex sample. Thestored lookup data of known device performance and known speciessignatures may be accessed for either single mode or simultaneous modedetections. By comparison with historical detection data for the device,these peaks can be clearly identified as the tell-tale spectra of themercaptan. Both spectra give clear indication of the mercaptan,qualitatively and quantitatively. Running both modes simultaneouslyclearly identifies the sample with unique and definitive detection datawhich can be compared to and matched with stored data to identify thedetected ions.

Thus it will be appreciated that the present invention is capable ofreal-time analysis of a complex sample, such as one containingmercaptans and hydrocarbon gas, because these ions are relatively of thesame mobility and can pass through the filter under the same fieldconditions.

Simultaneous positive and negative mode detection in a single mobilityscan thus provides a richness of detection data. This increasedidentification data results in a higher level of confidence, and reducedfalse positives, in compound identification. This is a valuableimprovement over the simple prior art FAIMS method of peakidentification.

The data that can be obtained from a negative mode scan is normallydifferent from that of a positive mode scan. While identification of acompound may be achieved by using one mode only, the used of detectionsfrom both modes makes for a more definitive identification with lowerlikelihood of error.

D. Improved Processing of Detection Data

The foregoing demonstrates favorably obtaining multiple detection datafrom a single mobility scan for positive identification of detected ionspecies in a sample. This innovation is useful in many applications.Notwithstanding this valuable innovation, we also can obtain a stillhigher level of confidence, and further reduced false positives, by (1)obtaining multiple detection data from multiple mobility scans, and (2)further processing such data to extract device independent attributes,such as a mobility coefficient, α.

1. Multiple Detection Data from Multiple Mobility Scans.

In this “multiple scan” embodiment, ions are identified based on not asingle set of field conditions, but based on multiple intensity datadetected at at least two and possibly additional numbers of high fieldconditions (i.e., at at least two field measurement points). Detectionsare correlated with the applied RF voltage and compensation, at the atleast two different field conditions, to characterize a given detectedcompound. Because multiple detection data are associated with a givenion species of interest, more accurate detections can be made.Comparison with stored data results in reliable identification ofdetected compounds.

Strategies for identification of detected ions based on data in spectralpeaks or in mobility curves include: curve matching, peak fitting, anddeconvolution (for overlapping peaks), and like techniques. Thesetechniques enable identification of detected ion species based peaks ina single scan, including simultaneous positive and negative modedetections, and also in multiple scans. The goal is the same:identification of multiple detection data that can be used todefinitively identify the species of a detected ion.

More particularly, we have observed that different ion species ofchemicals exhibit different mobility as a function of the compensatedapplied RF peak voltage that generates the high field conditions. Thus,by applying a set of different RF peak voltages and measuring thecompensation voltages at the peak locations for the various compounds,we can develop a family of measurement points characteristic of acompound. This family of points can then be plotted to determine themobility curve signature for specific species as a function of RF peakvoltage and compensation. We can record such data and use it forcomparison and identification when future detections are made of unknowncompounds.

Furthermore, we can extract field condition data, e.g., field strengthand compensation voltage for two nearby detections of the same ionspecies. We can then calculate the mobility curve, or at least the signand slope of the curve between those two data points as a signature ofthe detected ion species. We can simply store this data as the signatureof that compound along with the field conditions that generated suchdata. In the future, when two nearby or associated peak detections aremade for that species, we again know the field conditions and cancompute the sign and slope, or other mathematical variables representingof the curve, for comparisons to the stored data for match andidentification. This approach is successful with a high degree ofreliability; more complete curve matching is possible but is notrequired.

As will be appreciated by a person skilled in the art, the selection ofmeasurement points and the number of measurement points may be adjustedfor the specificity required for a particular application. The minimumnumber of measurement points is two, which at least identifies an aspect(such as slope) of the characteristic curve for a compound, given theknown field values.

As shown in the multiple scan data collected and recorded in FIG. 1C(prior art), each compound has a unique characteristic mobility curvethat expresses the peak detection data associated with that compound ateach of various associated peak RF and compensation values. Thus,detection of four different chemical compounds is shown includinglutidine, cyclohexane, benzene, and a chemical agent simulantdimethyl-methyl-phosphonate (DMMP). Each curve shows detection peaks atthe various field conditions that is characteristic for the compound.

The plot of compensation voltage versus dispersion voltage (i.e., RFpeak voltage) in FIG. 1C shows the associated compensation voltage forthe spectral peak for each of the particular compounds illustrated at agiven RF peak. As is seen from the plot, there is a region (indicated byreference numeral 100) in which the response for DMMP and cyclohexanemore or less overlap with one another (i.e., their mobility curvesoverlap). Therefore, operating in a peak RF voltage region of fromapproximately 2,500 to 2,650 volts, at around −6 to −8 voltscompensation, one would find it impossible to discriminate between thetwo compounds upon a single scan. In other words, the conventionalspectral scan would plot the overlapping peaks as a single peak at thatfield condition. Peak matching here would be inadequate, except forfurther software “tweaking” required to separate the peaks. However,this tweaking might not be matched by the stored data of a limitedlookup dataset, and therefore identification could fail. This certainlyis possible in a portable device that has real world size, space,computing power or other limitations.

We have recognized that by taking a look at an overall response of aFAIMS system to a range of RF peak voltages, over a range ofcompensation voltages, for a given chemical sample, we can note thateach of the curves exhibits a unique signature of field behavior. Wecall this mobility behavior a signature mobility behavior, and canidentify the compounds by this signature behavior.

It will thus be appreciated that a preferred practice of the presentinvention contemplates stepping the RF peak voltages and scanning thecompensation voltages to generate unique sets of data that identify anddistinguish the detected compounds to create a data store of mobilitysignatures. We then have a data to store for lookup that characterizesthese mobility curves and can be used for compound identification. Thisprocess will be explained in greater detail in connection with FIGS.10–10F.

We have discovered, therefore, that identification and quantification ofunknown chemical species can be improved by generating, for eachspecies, an experimentally determined curve of mobility versus appliedelectric fields. However, rather than comparing simply the peak observedmobility versus electrical field, mobility is determined over a range ofcompensated fields, possibly including relatively low voltage fieldstrengths (where mobility may be the same for some compounds) andincluding relatively high electric field strengths (where mobility isgenerally different for many chemical compounds). Comparison of aspectral curve or mobility curve generated with the detected data may bemade against stored curve data for positive identification.

Thus, by looking at a trend, i.e., the shift of the spectral peak andassociated compensation voltages from the first to second fieldconditions, we can better confirm the identity of the compounds. Inother words, other chemical compounds would not have the samecombinations of shifts at the same data locations, so that accurateidentification is made more likely.

For a generalized example, refer to FIGS. 4A and 4B, showing detectionintensity (abundance) as a function of compensation voltage at aparticular applied field strength. Note in FIG. 4A that peaks 110-1,110-2, 110-3, and 110-4 occur at a given Vcomp, with Vrf at 1400v (witha field strength of 28,000v/cm). Accordingly, as Vrf is changed to 1450v(field strength of 29,000 v/cm), shown in FIG. 4B, the set of peaksshifts to location at different Vcomp. Thus it is clear that applyingeven a slightly different field condition will result in peak locationsbeing at least slightly displaced, as indicated by shifts in associatedcompensation level. These observations can thus be used in a process ofidentifying detected ion species by collecting RF and Vcomp levels andcorrelating with detection data and then performing a comparison withstored identification data for known ions species. Upon making a matchor near match, an identification of the detected species can be made.

It will now be understood that it is possible to control fieldconditions and to discriminate between compounds that are ordinarilydifficult if not impossible to separately identify by other means.Selection of field conditions enables isolation of an ion species ofinterest. Furthermore, because the system of the invention matchesdetection data with stored data, we can select field conditions thatwill produce detection data that is matchable to stored data, assumingthe relevant ion species is present in the sample.

Turning to FIGS. 5A and 5B, we demonstrate the selectivity available inpractice of the present invention. In FIG. 5A, in a field strength of24000 v/cm, peaks for three different isomers of xylene in a sample, p-,o-, and m-, were detected. In FIG. 5A, the peaks for p- and o- areindistinguishable while the peak for m- is well defined. In order tofurther evaluate the sample, we perform a second detection, shown inFIG. 5B in a lower field strength of 18000 v/cm, where peaks for thethree different isomers of xylene are clearly distinguished andidentifiable.

It is therefore an additional recognition of the invention that betterdiscrimination between species is not always a result of higher fieldconditions, as. In fact, in this example, the p- and o-xylene isomersbecame distinguishable at reduce field strength. Again, now speciesidentification is by table lookup, preferably of multiple detectiondata, and regardless of whether based on an increasing or decreasing setof field conditions.

What is important to recognize here is that simply increasing the fieldstrength does not necessarily increase resolution as has been suggestedby others (see U.S. Pat. No. 5,420,424). In fact, to check for thepresence of a combination of compounds (or of isomers), or uponcollection of detection data that suggests such presence, multipledetection data may be collected and used together to form a signaturefor the detected ions. Now comparison to stored data may provideidentification of a single species or may provide identification of atypical grouping. For example, the detection data represented in FIG. 5Aor 5B alone are each characteristic plots of the three xylene isomers;alone these plots enable some identification but together they enable avery high degree of assurance that the three xylene isomers have beendetected. Therefore, a match to stored data for both field conditionsfor these isomers would provide a reliable ion species identificationwith low likelihood of false positives. Furthermore, a hand-held devicethat merely looks at these two or similar “data points” would bedelivered in practice of the invention as a handy xylene detector.

In another example of the invention, we generate detection data over arange of applied field conditions. For example, in FIGS. 6A and 6B weshow the effect of changes in field strength on the location ofdetection peaks at different compensation levels for hexanone andoctanone. These figures present a series of plots of the response of aFAIMS device with different applied field strengths. The curves areoffset on the vertical axis, with the offset increasing as electricfield strength increases. While various operating ranges are possible,as an illustration, FIGS. 6A and 6B may be understood as presenting thepeak RF between a low of around 620 volts (lowermost plot in each) and ahigh of around 1450 volts (uppermost plot in each). Several attributesare noted in this series of responses. For example, paying attentionspecifically to the hexanone plot of FIG. 6A, a monomer peak of 601-1 ofparticular interest is somewhat obscured in the lowest field strengthcondition. However, at the highest applied field strength, the peak601-m corresponding to hexanone is clearly discernable from the otherpeaks.

Several phenomena have occurred with the increase in increasing appliedfield strength. First, we note that a reactant ion peak (RIP) 605-1 wasrelatively dominant in the low field voltage reading. However, aselectric field strength is increased, the RIP 605-m shifts to the leftat a more rapid rate than the monomer ion peak 601-m of interest. Thisis because the α parameter, of the mobility coefficient for the reactantion species, is different than the α parameter for the monomer ion ofinterest.

In addition, we note that the relative amplitude of the reactant ionpeaks 605 decreases markedly with the increase in the electric field.Thus, RIP 605-m is observed at much lower amplitude and well separatedfrom the monomer peak 601-m of interest at a specific field condition.While the monomer peaks 601 also shift, they do not shift by the sameamount, or even as much. Thus, by analyzing the compound over a range ofapplied field conditions, a condition can be discovered at which the RIP605 will shift away from, or perhaps even shift off the scale of, otherobserved peak voltages. In some cases this allows easier detection ofthe monomer ion peak 601 of interest.

Similar behavior is observed in the monomer peaks 610-1, 610- . . . ,610-n observed for octanone and the resulting reactant ion peaks 615-1to 615-m. This information can thus be used to identify a species bycomparing a family of response curves to a stored family of knownresponse curves.

Another observed effect in both FIGS. 6A and 6B is that a so-calledgroup of cluster ions 608, 610 are seen. The cluster ions 608 representclusters of chemical materials in the sample. Typical cluster ions,having a heavier chemical weight, have peaks that are shifteddifferently from monomer ion peaks of interest. In particular, giventhat they are heavier, the cluster peaks shift differently. In thisexample, the cluster peaks shift in a direction away from the directionof shift of the monomer peaks with increasing applied field strength.This characteristic feature of cluster ions observed with this samplecan also be stored and utilized in recognizing the hexanone or octononeions.

These curves shown in FIGS. 6A and 6B are but one example of howapplying a range of field conditions to detect a given sample can beutilized to advantage. Another effect can be observed with theapplication of relatively high field strengths. Specifically, complexion groupings can be fragmented with higher field strength so that thecomponents of the group themselves can be individually detected.

For example, Sulfur hexafluoride (SF6) can be very well detected in thenegative mode. However, the response in the positive mode, while alonenot definitive, has a profile and thus in combination with the negativemode is confirmative and provides a lower likelihood of falsedetections. We therefore can detect SF6 in the single mode of dual mode,seriatim or simultaneously.

SF6 gas is used in atmospheric tracer applications to monitor air flow,as a tracer for leak detection in pipes to point detect sources ofleaks, in power plants to isolate switches to reduce, or preventbreakdown of the switches, among other uses. Isolation and detection ofSF6 is often found to be a difficult proposition.

In practice of the present invention, it is possible to detect SF6 inair, getting a very distinct peak for the SF6 separate from the reactantion peak. The reactant ion peak is composed of the ionized nitrogen andwater molecules in the air.

In conventional IMS (time of flight) the reactant ion peak overlaps theSF6 peak. In practice of the present FAIMS innovation, in the negativeion mode (i.e., detecting negative ions passing though the FAIMS filterbased on RF and compensation as shown in examples below), it is possibleto clearly separate between the SF6 peak and the reactant ion peak(RIP). This success in the negative mode separation between SF6 and theRIP peaks is clearly shown in FIG. 3C. However, in the positive ionmode, there is no detected difference between the signal without the SF6present and with the SF6, as shown in FIG. 3D.

In FIG. 3E, there is a plot of the FAIMS response at different RFvoltage levels in the negative ion mode. FIG. 3F shows this result andalso shows the RIP detected in absence of SF6. Thus clear vitality ofthe FAIMS filter of the invention with appropriate selection of RF andcompensation voltages is shown. In both cases the SF6 peak is shiftedfrom and distinct from the RIP.

FIG. 3G shows that FAIMS response in the positive ion mode (detectingpositive ions passing through the FAIMS ion filter), where the SF6 peakis not isolated from the RIP. While alone this is not definitive, it isan expected detection and therefore may be used as confirmative whencombined with a definitive SF6 negative mode detection.

In one embodiment of the invention a portable battery powered unit forthe detection of SF6 with a sensitivity of 1×10−9 atm cc/sec SF6 (0.01PPM) is enabled. In this embodiment, the invention may be used, forexample, in the power industry to ensure the leak tightness of HighVoltage Switchgear and in the laboratory for testing fume hoods to theASHREA 110 specification. Other applications include torpedo head,pipework systems, and air bag integrity testing. The high sensitivity,rugged design and ease of use and set up of the invention areadvantageous for many applications that involve the detection of SF6.

FIG. 7 is an example of such an affect on a mercaptan ion sample. Inparticular, a range of background voltages (from 620–1450 volts) wereapplied to an ethyl mercaptan spectra in which we see a general shift ofion peak behavior as an electric field conditions are strengthened.However, we also observe a fragmentation condition. Specifically, atlower applied field conditions, strong single peak is observed, such asat 701-1. However, as electric field strength is increased, multiplepeaks 701-n, 702, . . . 710 are observed in a spectra. By observing andrecording the peak locations not only at the low volt field conditions,but also at a range of field conditions, this fragmentation behavior canbe further exploited to better identify compounds. We can store dataindicating the peak RF voltage at which fragmentation occurs, or thelocations of the fragment peaks, and then further use it when matchingdetection data.

We have also been able to discover species identification method that isdevice-independent. Turning now to FIGS. 8A and 8B, we have plottedexperimental detection data recorded in Table 1 (FIG. 8C) for ahomologous group of ketones, including: acetone, butanone, pentanone,hexanone, heptanone, octanone, nonanone, decanone (8A—monomers,8B—clusters). Each species has a unique mobility curve, and thus aunique mobility signature, for the given set of field conditions. We canstore this data and then use the same device as a detector for ketones.We obtain a set of detection data and perform curve matching versus thestored data or other data comparison. A match enables identification ofthe detected ketone in that device. We also can take any two sets ofpoints and store curve data, such as slope and sign, for theexperimentally detected data for a known species. Now with twodetections, such as at peak RF field strengths (E) of 28000 and 29000v/cm, we have two data points, between which we can compute slope andsign for a purported connecting curve function, and then we compare tostored data to make a positive identification of a detected species inthat device.

However, we can go a step further by making the identification processdevice-independent. Thus we create data that can be used in any systemthat detects field mobility dependence of an ion. This is based ondetermining the parameters of a function derived from the fundamentalmobility coefficient associated with each species.

Therefore, for example, the multiple data represented in FIGS. 4A and 4Band 5A and 5B each can be used to provide positive identification of adetected species by the unique and inherent mobility characteristic thatidentifies that species. We make this comparison to a lookup table thatcan be specific to the device in question, but also can be a universalset of data that is device-independent. Thus, in general, one does notwish to only compare the plot of abundance curves versus compensationvoltage individually, but rather generate a plot of observed peaklocations for specific compensation voltages, so that curves, slopes,signs, and various details can be discerned for each of the detectedions for comparison to a library of lookup data.

2. Alpha Coefficient Determination

More specifically, in computing mobility signatures, we have found thatan expression of the field-dependence of ion mobility, the so-called αcoefficient, expressed as a function of field, can be used to generate aunique α function that is inherent for that species and is deviceindependent. Thus the α function can be used as the unique signature ofa species; quite remarkably, this function expresses both acharacteristic signature for the ion species and is device independent.In short, we recognize that peaks change position in signature waysbecause they have different alpha signatures.

Thus we use the α function as a mobility signature for detected species.The signature can be determined for a detected unknown compound based onthe field conditions that are used, and then this can be used to make anidentification according to a lookup table of stored known signaturedata associated with known compounds. More particularly, in practice ofa preferred embodiment of the invention, ion species are identifiedbased on the mobility dependence of the species under various fieldconditions. Data is collected for the sample under test for at least twofield conditions, the data is processed, and a comparison of detectiondata computed as an α function for the sample under test versus thestored data enables identification of the compounds in the sample.

Referring again to the discussion of the α parameter, FIG. 1B is a plotof mobility versus electric field strength for three examples of ions,with field dependent mobility (expressed as the coefficient of highfield mobility, α) shown for species at a greater, equal to and lessthan zero. For any given set of field conditions, the field strength andcompensation can be correlated with an α value. This is shown in thework of Buryakov et. al., A New Method Of Separation Of Multi-AtomicIons By Mobility At Atmospheric Pressure Using A High-FrequencyAmplitude Asymmetric Strong Electric Field, Intl J MassSpec and IonProc. (1993), at p. 145.

We have observed that knowing the a parameter alone at a particularfield strength does not prevent false positives. This would occur at theintersection of the two plots in FIG. 1C, at the point indicated byreference numeral 100. Without more information, knowledge of the αparameter for the respective ion species at that location does notprovide unique mobility signatures for both compounds. Thus, withoutdoing more, any number of readings at this intersection is likely toresult in a detection error.

However, we have also found that we can express an ion's α mobilitycharacteristic as a function of field, i.e., as α(E), and can define aunique mobility signature for the ion species which isdevice-independent. This α(E) or “alpha function” relates the size,effective cross-section, shape, and mass of the ion to field conditions.It is understood that as the applied electric field increases, theincreasing electric field tends to displace, stretch, and/or breaks thebonds of the ion such that the stronger the field, the greater theinduced dipole, quadripole, or higher order moments of the ion. These,in turn, affect the relative mobility of the specific ion. The result ofrelating these aspects is to define a unique mobility signature for theion species of interest. This also turns out to be device-independent.

The relationship of the α(E) function to field conditions is shown inthe following:

$\begin{matrix}{{V_{c}(E)} = \frac{< {\alpha\; E_{s}{f(t)}} >}{{1 +} < \alpha > {+ {< {\frac{\mathbb{d}\alpha}{\mathbb{d}E}E_{s}{f(t)}} >}}}} & (1)\end{matrix}$where: Vc-compensation voltage (peak position); Es-electric fieldstrength; f(t)-waveform parameters (waveshape and so forth).

Thus for each spectral detection, we can compute α as a function offield conditions, i.e., α(E). Specifically, the asymmetric waveform in afield asymmetric waveform mobility spectrometer, E_(max)(t)=E_(max)f(t),is designed to satisfy the following conditions:

$\begin{matrix}{{{1/T}{\int_{0}^{T}{{E_{s}(t)}{\mathbb{d}t}}}} = {< {E_{s}{f(t)}}>=0}} & \left( {3a} \right) \\{< {f^{{2n} + 1}(t)} > \neq 0} & \left( {3b} \right)\end{matrix}$where ƒ(t)—is a normalized function which describes the waveform, andE_(max) is the maximum amplitude of the waveform. The waveform isdesigned such that its average value is zero (equation 3a) while thepolarity of the electric field during one period is both positive andnegative. The addition of the compensation field, C, to the waveformE_(s)(t) yields Equation 4:E(t)=E _(s)(t)+C=E _(s)ƒ(t)+C  (4)so the average ion velocity over a period of the asymmetric waveform canbe written as:V=<V(t)>=<K(E)E(t)>  (5)Only ions with average velocity of zero, v=0, will pass through the gapwithout neutralization. An expression for the compensation fieldrequired to enable an ion to pass through the gap can be obtained bysubstituting Equations 2, 3, and 4 into Equation 5 as shown in Equation6:

$\begin{matrix}{C = {\frac{< {\alpha\; E_{s}{f(t)}} >}{{1 +} < {\alpha.} > {+ {< {\frac{\mathbb{d}\alpha}{\mathbb{d}E}E_{s}{f(t)}} >}}}.}} & (6)\end{matrix}$The value of this compensation electric field can be predicted preciselywhen the alpha parameter for the ion species, the waveform ƒ(t), and theamplitude of the asymmetric waveform E_(max) are known.

A procedure for extraction of α(E) from experimental measurements of theelectric field dependence of the mobility scans is thus known. In thissection, some additional considerations regarding the alpha parameterand methods to determine this parameter described. First, emphasis mustbe given that the alpha parameter is a function (not a number) and thephysical and chemical information about an ion is contained in the shapeof the α(E) curve. The method of representing this curve is incidentalto the topic. The only criterion critical in these methods is that thecalculated values for mobility (i.e. K(E)=K_(o){1+α(E)]) should be asclose as possible to the experimental values. The function for α(E) canbe represented as an even power series or in complex form. In eitherinstance, the curves of experimental results and calculated should agreeclosely. Thus, the quality of the approximation is limited by theaccuracy of the experimental results and has been illustrated.Discerning the quality of a model based upon two parameters, threeparameters, or a nonlinear function with five parameters was difficult.All approximations were located within the error of ΔC₁ (at ±9%).

In this work, a simple uniform method is described to represent thefunction of α(E), which will be suitable for comparison of resultsobtained under different experimental conditions. These methods could beused for differing asymmetric waveforms or different designs of IMSdrift tubes: linear, cylindrical, or planar FAIMS. In general then, thecriteria for choosing the level of approximation of alpha is first toensure that the method of extracting the alpha parameter uses the leastnumber of individual parameters of the experimental device. Second, theresult should contain the fewest number of adjustable parameters, andthe approximation curves should be within the experimental error bars.In the next section, the general method to extract the alpha parameteris described and then applied in the subsequent section.

The function of α(E) can be given as a polynomial expansion into aseries of electric field strength E degrees as shown in Equation 7:

$\begin{matrix}{{\alpha(E)} = {\sum\limits_{n = 1}^{\infty}{\alpha_{2n} \cdot E^{2n}}}} & (7)\end{matrix}$Substituting Equation 7 into Equation 6 provides a value of thecompensation voltage as shown in Equation 8 where an uneven polynomialfunction is divided by an even polynomial function. Therefore an odddegree polynomial is placed after the identity sign to approximateexperimental results:

$\begin{matrix}{C = {\frac{\sum\limits_{n = 1}^{\infty}{\alpha_{2n}S^{{2n} + 1}\left\langle {f^{{2n} + 1}(t)} \right\rangle}}{1 + {\sum\limits_{n = 1}^{\infty}{\left( {{2n} + 1} \right)\alpha_{2n}S^{2n}\left\langle {f^{2n}(t)} \right\rangle}}} \equiv {\sum\limits_{n = 1}^{\infty}{c_{{2n} + 1}S^{{2n} + 1}\left\langle f^{{2n} + 1} \right\rangle}}}} & (8)\end{matrix}$This allows the a comparison of the expected coefficient (approximated)to be compared to the values of alpha parameter as shown in Equation 9:

$\begin{matrix}{c_{{2n} + 1} = {{\alpha_{2n}\left\langle f^{{2n} + 1} \right\rangle} - {\sum\limits_{k = 1}^{n - 1}{\left( {{2\left( {n - k} \right)} + 1} \right)c_{{2k} + 1}\alpha_{2{({n - k})}}\left\langle f^{2{({n - k})}} \right\rangle}}}} & (9)\end{matrix}$Alternatively, alpha parameters can be calculated by inverting theformula by using an approximation of the experimental results perEquation 10:

$\begin{matrix}{\alpha_{2n} = {\frac{1}{\left\langle f^{{2n} + 1} \right\rangle}\left\{ {c_{{2n} + 1} + {\sum\limits_{k = 1}^{n - 1}{\left( {{2\left( {n - k} \right)} + 1} \right)c_{{2k} + 1}\alpha_{2{({n - k})}}\left\langle f^{2{({n - k})}} \right\rangle}}} \right\}}} & (10)\end{matrix}$

Any number of polynomial terms (say 2n), in principle, can be determinedfrom Equation 10 though a practical limit exists as the number ofpolynomial terms in the experimental result of the approximationc_(2n+1) should be higher than the expected number of alpha coefficientsα_(2n). Since the size of n depends on the experimental error, the powerof the approximation of the experimental curves C(E_(s)) cannot beincreased without limit. Usually N experimental points of C_(i)(E_(si))exist for the same ion species and experimental data can be approximatedby the polynomial using a conventional least-square method. Finally, thenumber series terms cannot exceed the number of experimental points soincreasing the number of series terms above the point where the fittedcurves are located within the experimental error bars in unreasonable.In practice, two or three terms are sufficient to provide a goodapproximation shown in prior findings. The error in measurements must bedetermined in order to gauge the order of a polynomial for alpha. Thesources of error in these experiments (with known on estimated error)were:

-   -   1. Error associated with measurement and modeling of the        RF-field amplitude (˜5%);    -   2. Error in C(E_(s)) from a first-order approximation of        Equation 4 (˜3%), and    -   3. Error in measuring the compensation voltage (˜5–8%).        An approximate error may be ˜10% and there is no gain with        approximations beyond two polynomial terms; thus, alpha can be        expressed as α(E/N)=1+α₁(E/N)²+α₂(E/N)⁴ with a level of accuracy        as good as permitted by the measurements.

A standard least-square method (regression analysis) was used toapproximate or model the experimental findings. For N experimentalpoints with C_(i)(E_(si)) and for C=c₃S³+c₅S⁵ a function y=c₃+c₅x can bedefined where y=C/S³; x=S² so c₅ and c₃ are given by Equations 11 and12, respectively:

$\begin{matrix}{c_{5} = \frac{{\sum\limits_{i = 1}^{N}{x_{i}{\sum\limits_{i = 1}^{N}y_{i}}}} - {N{\sum\limits_{i = 1}^{N}{x_{i}y_{i}}}}}{\left( {\sum\limits_{i = 1}^{N}x_{i}} \right) - {N{\sum\limits_{i = 1}^{N}x_{i}}}}} & (11) \\{c_{3} = {\frac{1}{N}\left( {{\sum\limits_{i = 1}^{N}y_{i}} - {c_{5}{\sum\limits_{i = 1}^{N}x_{i}}}} \right)}} & (12)\end{matrix}$Through substituting experimental value c₃, c₅, values for α₂ and α₄ canbe found per Equations 13 and 14:

$\begin{matrix}{\alpha_{2} = {c_{3}/\left\langle f^{3} \right\rangle}} & (13) \\{\alpha_{4} = \frac{c_{5} + {3c_{3}\alpha_{2}\left\langle f^{2} \right\rangle}}{\left\langle f^{5} \right\rangle}} & (14)\end{matrix}$In order to calculate α_(2n), knowledge is needed for the approximationsof experimental curves for C(E_(s)) and for the function ƒ(t)—which is anormalized function describing the asymmetric waveform.

For example, nine data points were identified for each of the eightketones of FIG. 8, based on the data collected in Table 1 of FIG. 8C.These can be used to compute the α curve for that species, such as witha piecewise linear approximation to the α curve. For example, two datapoints for butanone are a(Vcomp-a, Vrf-a) and b(Vcomp-b, Vrf-b). Betweenthese two points, the slope and sign of the butanone curve can becomputed. More complete characterization of the curve, such as withpolynomial curve fitting, is also possible.

Now this data set becomes part of a data store for use in identificationof the species of an unknown detected ion species for which two datapoints are collected and the corresponding curve data is computed. Inshort, in a simple practice of the invention, we collect data on atleast two closely associated points (peaks) for a given ion sample andgenerate the curve data accordingly. Once we have the detected andcomputed data, we assume this approximates the alpha curve and thereforedo a lookup to our stored data. Upon finding a match, we can thenpositively identify the sample.

In FIGS. 9A and 9B (monomers and clusters, respectively) we computedunique α curves for ketone ions (acetone, butanone, pentanone, hexanone,heptanone, octanone, nonanone, decanone) based on data collected in theFIG. 7B Table, plotting the percent change in a against the change offield strength for the various data collected ion Table 1 (FIG. 8C).These plots of percent change in α against field strength express aunique signature for each of these ion species. This is loaded in ourdata store for later comparison: the signature data includes the RFfield strength and the compensation voltage at which the peak isdetected, we also associate with it the identifying data for the known αfunction associated with that detected peak location and fieldconditions for each species.

FIGS. 9A and 9B thus express the α function for individual ketonesspanning electric fields of 0 to 80 Td (˜23 kV/cm), expressed as apercentage change in alpha as a function of field conditions. Theseplots are fundamental signature features of these ion species that areindependent of the drift tube parameters and can be used in othermobility spectrometers. Thus the α function can be favorably used inpractice of the invention to provide a mobility identification data setthat is device-independent.

These results are surprising and demonstrate that for chemicals with thesame functional group, protonated monomers of a single type exhibit abroad range of behavior vis-à-vis the dependence of coefficients ofmobility on electric fields. This difference in behavior for a commonmoiety suggests that the effect from the electric field must beassociated with other aspects of molecular structure. One possibleinterpretation is that ions are heated during the high field and theeffect on the protonated monomer should be striking. These ions withstructures of (H₃O)⁺M (H₂O)_(n) or perhaps (H₃O)⁺M (H₂O)_(n)(N₂)₂,should be prone to dissociations with slight increases in iontemperature caused by the high field conditions. Thus, ioncross-sections and mobilities would accompany declustered small ions athigh fields.

Referring again to FIG. 9A, it will be noted that there is approximatelya 20% increase in α(E) for the protonated monomer of acetone with highfields. As the molecular weight of the ketone is increased, ion heatingshould be less pronounced and reflected in the α(E) function. The α(E)function for proton bound dimers (clusters) is consistent with decreasesin mobility under high field conditions. Consequently, the basis for theα(E) function differs from that of protonated monomers. Indeed, theproton bound dimer for decanone undergoes a 5% decrease at high fields.The cause for a decrease in mobility at high fields has no existingmodel but should be due to increased collisional size or increasedstrength of interaction between the ion and the supporting gas.

Furthermore, if we were to do the same for the cyclohexane and DMMP inFIG. 1C, the computed alpha curves would differ accordingly. In thismanner, we can distinguish ion species even when their mobility curvesoverlap, as long as we have at least a second detection data set toassociate with each detected species in question. Therefore we achieve ahigh level of assurance for the accuracy of our identifications.

Thus we have shown that the fundamental dependence of mobility for ionsin high electric field can be obtained from field asymmetric ionmobility spectrometry. Functions of dependence can be extracted fromexperiments using known methods to treat imperfect waveforms. Thesefindings show an internal consistency with a homologous series ofketones, and also indicates a mass dependence not previously reported.

Now it will be appreciated that in practice of the invention, ionspecies are identified based on ion mobility dependence of the speciesunder various field conditions. First, characteristic changes in ionmobility, based on changes in field strength and field compensation, arerecorded and stored for a library of known compounds; secondly data iscollected for the sample under test for a variety of field conditions;thirdly, a comparison of detection data for the sample under test versusthe stored data enables identification of the compounds in the sample.The quality of stored data and strength of the mobility relationshipenables improved species identification.

It should be furthermore understood that the invention is applicable notonly to one type of field asymmetric ion mobility system but may beapplied in general to ion mobility spectrometry devices of varioustypes, including various geometries, ionization arrangements, detectorarrangements, and the like, and brings new uses and improved resultseven as to structures which are all well known in the art. The presentinvention is not limited to configurations of the examples and may bepracticed in any other configurations, including plate-type, planar,radial, spherical, or cylindrical FAIMS devices. Furthermore, inpractice of an embodiment of the invention, the output of the FAIMSfilter may be detected off board of the apparatus, such as in a massspectrometer or other detector, and still remains within the spirit andscope of the present invention.

The foregoing discussion has been focused on detection andidentification of species of ions. However, this invention is broaderand can be applied to any system for identification of unknown speciesof ions traveling through a varying controlled excitation field, theidentification being based on the known characteristic travel behaviorof the species under the varying field conditions. The ion or ions to beidentified may be traveling alone or in a group of ions of same ordiffering characteristic travel behavior. The field may be compensatedin any of various manners as long as a species of interest is returnedto the center of the flow and permitted to pass through the filter whileall other species are retarded or neutralized. Identification is madebased on known field-dependent differential mobility behavior of atleast one species of ions traveling in the field at known fieldconditions.

E. A Process for Identification of Compounds

Focusing attention now on FIGS. 10A–10F a specific sequence of stepswill be described that may be carried out to perform speciesidentification in several of the embodiments of the present invention,which are provided by way of illustration and not limitation. In thisillustration, the sequence of steps would be performed by themicroprocessor 46 which is associated with the ion mobility spectrometerdevice 10. As was already described in connection with FIG. 2 therewould also be an RF voltage generator 42, compensation voltage generator44, a memory 47 and an analog to digital converter 48. Themicroprocessor 46 provides digital control signals to the RF dispersionvoltage generator 42 and compensation voltage generator 44 to controlthe desire drive voltages for the filter 24. These may also include forexample, digital to analog converters that are not shown in detail inthe drawings here.

The microprocessor 46 coordinates the application of specific RFdispersion voltages Vrf and compensation voltages Vcomp also taking intoaccount the function of observing responses from the detector 26 as readthrough the analog to digital converter 48. By detecting attributes(such as the peaks) of observed abundances of a particular ion speciesacross a range of Vrf voltages, the microprocessor 46 can thus takesteps to identify particular compounds. These may include, for example,comparing or correlating particular “response curve” data against alibrary of response curve data as stored in the memory 47. They can alsoinclude computation of α curve parameters. The results of the comparisonoperation can be provided in the form of an appropriate output devicesuch as a display or personal computer or the like, or maybe provided byelectrical signals through an interface to other data processingequipment.

As shown more particularly in FIG. 10A, a state 1000 is entered into themicroprocessor 46 in which a compound is to be analyzed. Here, thecompound is known and identified, such as by a user supplying anidentifying text string to the computer. A sequence of steps is thenperformed by which data is to be acquired concerning the known chemicalcompound. From this state 1000 a next state 1002 is thus entered inwhich a range of dispersion voltages Vrf and compensation voltages Vcompare determined by the processor 46. These ranges include a beginningvoltage (b) and an end voltage (s) and step voltage(s) to be applied toeach of the ranges Vrf is thus varied from an initial value Vrf(b) to afinal value Vrf(e) by a step amount Vrf(s). Similarly, Vcomp is to bevaried from Vcomp(b) to a final value Vcomp(e) by a step amountVcomp(s).

The voltage ranges are then applied in the following steps.Specifically, step 1004 is entered in which the Vrf is allowed to stepthrough a range of values. A state 1008 is entered next in which thecompensation voltage Vcomp is also swept or stepped through a series ofvalues or ranges.

In state 1010 the response to each applied voltage is stored as a value,a.

If the last compensation voltage has not yet been tested then processingreturns to state 1008 in which the next compensation voltage is applied.However, in state 1012 if all of the compensation voltages have beenapplied then processing proceeds to a state 1014 wherein a test is madeto see if all of the dispersion have been applied.

The loop continues until all of the compensation and dispersion voltageshave been applied resulting set of data is then analyzed in a state 1018to identify features of interest. In a specific example being describedit will be the peak locations that are of interest. For each such peakin an observed response for a given applied dispersion voltage Vrf, aresponse value for a specific Vcomp is determined and its correspondingamplitude, a, is detected and stored.

The response curve data, or certain attributes thereof such as the peaklocations are then stored as a data object P (or table) as shown in FIG.10B. Such an object will typically contain an identification of thetested compound such a text string. Also stored of course are a set ofthe applied dispersion voltages Vrf. For each such dispersion voltageVrf a corresponding peak compensation voltage is stored. Specifically,what is stored is at least the compensation voltage Vcomp at which apeak was observed, and typically the corresponding amplitude of theresponse (abundance) observed at that peak.

It is by now understood by the reader that for a given RF voltage Vrfthere may actually be a set of compensation voltages at which a numberof “peaks” are observed. For example, as was described in connectionwith FIG. 6A the sample analyzed was made up of a compound of specificions monomers, cluster ion, and reactant ion peaks. Thus, there shouldbe an accommodation in the structure of object P to anticipate thatthere will be more than one peak observed in any particular mobilityscan, and that the number of peaks per response curve will not always bethe same number.

An example data element of object P is thus shown where for a single RFdispersion voltage, Vrf-1, peaks were observed at compensation voltagesVc11, . . . , Vc1 n having corresponding amplitudes a11, . . . , a1 n.Thus might correspond to the case of the lowest applied dispersionvoltage in FIG. 6A, where numerous peaks 601-, 605-1, 608-1 aredetected. However, at another dispersion voltage Vrf-m, only a singlepeak at Vcomp-m, am was detected. This might correspond to a case suchas in the uppermost curve of FIG. 6A, where only a single peak 601-m wasdetected.

In a typical application, a library of data objects P (referencevectors) would be developed by running the steps of FIG. 10A fordifferent known compounds.

This would then permit an instrument to eventually enter a chemicalrecognition state 1200 as shown in FIG. 10C. From this state a series ofmeasurements are taken in states 1202–1214 that are not unlike themeasurements taken in FIG. 10A. Specifically, a series of measurementsare taken for a specified compensation and RF voltages. It should beunderstood that an entire set of all of the same measurements need notbe taken in this mode as were taken in the chemical data acquisitionmode. Specifically, not all points on a relatively dense response curveneed to be taken, only enough to identify each compound.

Once the measurements are taken a state 1220 is entered in whichfeatures such as peaks of the response are identified for each peak acorresponding compensation voltage and amplitude may be identified andthese stored to a candidate measurement vector P′.

The candidate vector P′ thus represents a series of data that need to betested against a number of candidate compounds. The candidate vector P′is then analyzed in states 1230 and/or 1240 by looking up correspondingcounterparts in the library of reference vector objects P, and scoring amatch between P and P′. These steps may be iterated until such time as amatch or a best match is determined in a state 1250.

It should be understood that any number of techniques may be used todetermine a degree of match between P and P′. For example, if theelements (Vcomp, a) of P and P′ are considered to be data points inEuclidian geometry space, a distance can be computed. The comparisonwith the smallest Euclidian distance can then be selected as the bestmatch. However, other recognition techniques may be used or to determinean identify of an unknown compound, for example, are there moresophisticated signal processing techniques such as correlation may beused to resolve peaks; or other known pattern recognition algorithms,neural networks or artificial intelligence techniques may be used tofind a best match for P′.

This best match is then identified to a user such as by looking up thecompound identifier field and displaying in state 1260.

FIG. 10D shows a series of steps that may be added to the dataacquisition phase and the chemical recognition phase to take advantageof second order data processing characteristics. For example, in thedata acquisition state, a series of states 1020, 1022, 1024 and 1026 maybe added which attempt to curve-fit specific attributes of the measuredresponse. Specifically, a state 1020 may be entered in which for eachdata element of the object P a vector, z, is formed consisting of thepeak compensation voltages vc1, vc12, . . . vc1 m.

This vector is in fact a vector of point locations for the peaksobserved for a range of compensation voltages. Returning attention toFIG. 6A, briefly, this may correspond to for example locating the points601-1, . . . 601-m, . . . 601-n corresponding to peak height andlocations for the monomer ions of interest. A curve may then be fitthrough these peaks such as by applying a curve fitting algorithm, instate 1024. In the illustrated example it is assumed that a quadraticequation is fitting the peaks of the form y²=βx²+γ. The β and γcoefficients can then be stored in the state 1026 associated with thevector. The chemical is thus identified by a curve fit to its peaklocations approximating its mobility (α coefficient) behavior.

If this is done, a corresponding set of steps 1270, 1272 and 1274 wouldbe typically added to the chemical recognition process. Thus, peakswould be identified instead of comparing raw data values in states 1270and 1272 by performing a curve fit to observe data and then determiningγ and β coefficients. In state 1274 the β and γ coefficients would betested to determine closest matches in the P object library.

FIG. 10F shows a series of steps that may be used to identify ordistinguish peaks in the acquisition phase. Here initial data may beadded to the objects P by identifying peaks as a cluster peak or monomerpeak. Specifically, if a peak shift is observed as a range as a range offield condition voltages (e.g., Fog. 6A) is increased then this might beidentified as a cluster peak. If the peak does not meet specificshifting criteria it might be identified as a monomer peak. States 1310,1331, and 132 could thus be added to the identification process. Theresults of these steps would add an additional parameter L associatedwith each data point in the object P to further identify each peak as amonomer cluster or other peak type, as shown in FIG. 1E.

Other approaches to this could potentially be used to label peaks. Forexample reactant ion peaks could also be identified by running ananalysis on a response of the instrument when no sample is applied. Inthis mode only the reactant ion peaks would occur in their behavioracross a range of compensation voltages could be stored. In any event,information concerning the particular type of peak can thus be stored inthe pointer data in a state 1320 at which such a peak is detected. Thisinformation can then be added to the objects P specifically as shown inFIG. 10E.

FIG. 10G shows additional processing steps that might be performed inthe chemical recognition state to take advantage of the situation ofFIGS. 8A and 8B in which monomer and cluster ion behavior is observed.Specifically, these steps in FIG. 10G might be added as further steps1280 in the recognition phase. Here for every candidate peak P′corresponding monomer peak in the reference array P is compared. A scoreis then associated with the closest of the match in state 1284 similarlyin state 1286 a cluster peak may be compared with its corresponding inthe peak library P. A score sc is then determined in step 1288 dependingon the closest of this match. Finally, in a state 1290 a final score sfcan be associated with weighting the monomer peak score and the clusterpeak score by weighting factors wm and wc for example in an instancewhere cluster peaks are expected to provide more information thanmonomer peaks, cluster peaks might be weighted highly and monomer peaksrelatively low or zero factor. This weighting is understood now how bothmonomer and cluster peak identification can be combined to furtherrefine compound identification.

It will be evident to one skilled in the art that various modificationsand variations may be made to the present invention without departingfrom the spirit and scope herein. For example, although the apparatusillustrated in FIG. 2 has a single filter 24 and detector 28, it shouldbe understood that a series of filters 24 can be applied to a specificgas ionized sample S. The first can be used as a pre-filter to limitchemical species to a particular range of species that are know to be ofinterest, with the second filter in the series being used to provide fordetailed sweeping at precise incrementing voltages to provide forgreater resolution.

In a further embodiment of the invention we are able to separate anddistinguish between overlapping FAIMS spectra, with improved speciesidentification. Turning to FIG. 11A, we show two overlapping spectra forspecies A and species B, showing the change in mobility (Δk) as afunction of electric field (E). These spectra are essentiallyoverlapping. This may occur when two species are detected that haveidentical or very similar high field mobility characteristics.

It will be further appreciated that whle DMS devices have good range andspecies resolution, this is not true for every ion species. Species in aparticular frequency range, say 1–2 MHz may be difficult to resolve fora given system, say for molecules having weights of 300–700 AMU. Theseions tend to pass very close (i.e., have compensation voltage valuesvery close) to zero compensation. But by selectively passing ions withsuch compensation level through the DMS as a pre-filter and introducingthem into the IMS, these ions species can be resolved with added IMSdetection data. This technique can also be applied to separation andidentification of dimers, clusters and the like.

Now this IMS data can be used to identify the ion species or can beadded to DMS detection data to further improve species identification.This works for species that have similar high field spectra because itis likely or at least possible that the low field characteristics (basedon the low field coefficient Ko) of species will be different. Wetherefore obtain the low field detection data for overlapping speciesand then add this data to separate their spectra.

The low field data is essentially represented as a dc level. Forexample, species A might have a characteristic low field mobilityrepresented as dc value of −1 and species B might have a characteristiclow field mobility represented as dc value −2. Now each low fieldmobility parameter can be added to the detection data for that speciesas a dc-offset. FIG. 11B shows where the spectra A, B are each offset byan amount equivalent to their own associated dc-offset, resulting inspectra separation.

It is therefore a method of an embodiment of the present invention asdescribed above to detect both species-specific low field mobility (Ko)and high field mobility (ΔK) differences and to use this data to providedetection spectra with a high degree of species discrimination. We candetermine the parameters of K(E) by various means. For example, it ispossible to extract low field mobility by processing of DMS detectionspectra and then to add this to the DMS spectra as an offset to furtherseparate overlapping spectra.

It is also possible to obtain low field mobility data directly from anIMS spectrometer for a given sample under test and to add this IMS lowfield mobility data to the DMS spectra to obtain the improved detectionresult of FIG. 11B. This process combines the detection data normallyassociated with IMS with the detection data normally associated with DMSwith improved detection results. Now detection spectra may morecompletely represent the effect of the electric field, K(E), where theK(o) low voltage coefficient of mobility is obtaining in any manner, andthe high field differential mobility is obtained from the DMS.

Therefore use of IMS low field detection data with high field DMSspectra data has several advantages. Further provision of an integratedIMS/DMS system has several additional benefits as shown below. In apreferred embodiment, this is achieved wherein the DMS is a pre-filterto an IMS.

In conventional time of flight (TOF) IMS, ionized sample is held at gateand then released into a drift tube. The ions are conveyed down thedrift tube based on their mobility in a dc gradient between the shutterand an attractor electrode. The time of drift to the collector electrodeis related to the low field mobility of the detected ion species.However, the shutter mechanism, whether by field or mechanical, can becomplicated.

In one series of embodiments of the invention, DMS and IMS are combined,wherein their detection data are harnessed to provide improved speciesdiscrimination. In one approach, a DMS device, whether plate-type,cylindrical, radial, or otherwise, filters an ionized sample flowpreferably according to the improved field asymmetric ion mobilitypractices of the invention. The filtered stream passing out of the DMSfilter has been reduced down to an ion species, or perhaps one set ofspecies have overlapping spectra, based on high field mobilitydifferences. In further embodiment, this pre-filtered ion flow isfurther analyzed in a IMS device.

An illustrative embodiment of the invention is shown in FIG. 12A,wherein a DMS ion filter 2000 (such system 10 shown in FIG. 2,) ismodified to accommodate improved spectral separation. The ion filterregion 2002 is the same as earlier described, having ion filter 24 withion filter electrodes 20, 22. Filtering preferably proceeds based ondifferences in ion mobility in the filter field and thereafter thefiltered ion flow 2004 exiting the filter enters detector region 2006.

Detector region 2006, includes detector electrodes 2008, 2010. Now, asbefore, two species of ions 17+ and 17−, can be passed by the ion filterand can enter the detection region where further separation occursfollowed by species detection and identification.

As noted in regard to FIG. 2, detector 26 includes a first detectorelectrode 28 and a second detector electrode 30. These electrodes may bebiased to detect either negative or positive species. But electrode 28may be positively biased to attract ion 17− and to repels ion 17+, whileelectrode 30 may be biased negatively to attract ions 17+ whilerepelling ions 17−. It is a feature of this invention that where theseelectrodes are oppositely biased they may make simultaneous detectionsof positive and negative spectra.

It will be further appreciated that the separated ions deposit theircharges on the appropriately biased detector electrodes 28 or 30. Thesignals generated by the ions collecting at detector electrodes 28 and30 are amplified by respective amplifiers 36 and 38 to provide signalsto command and control unit 34.

In a further embodiment of the invention, a combined DMS withshutterless IMS detector system is provided. This arrangement may beused to selectively inject particular pre-filtered ion species into anIMS that has been tuned to a specific range or polarity.

As shown in FIG. 12A, detector electrodes 2008 and 2010 are provided toperform the function of detector electrodes 28 and 30 of FIG. 2.However, an orifice 2012 is formed in electrode 2008 and an orifice 2014is formed in electrode 2010. Now at least one IMS device, preferablytwo, devices are formed as part of apparatus 2000.

As shown in FIG. 12A, each IMS section includes a drift tube 2021, 2031,flow gradient electrodes 2022, 2032, an orifice 2023, 2033 for matingwith orifice 2012, 2014, such that IMS section 2020 is in fluidcommunication with orifice 2012 and IMS section 2030 is in fluidcommunication with orifice 2014. The IMS sections also include attractorelectrodes, 2024, 2034.

In a first mode of operation, as with the ion flow of FIG. 2, theseparated ions 17+, 17− deposit their charges on the appropriatelybiased detector electrodes 2008, 2010, wherein positive and negativeions are deflected to the oppositely charged detector electrodes,assuming that the IMS sections are not charged. Assuming that electrode2008 is negatively charged and electrode 2010 is positively charged,then ions 17+ will be driven toward electrode 2008 for detection andions 17− will be drive toward electrodes 2010 for detection. These ionsare detected when they deposit their charges on the appropriateelectrode.

This deposit process is changed however when the IMS sections areenabled. A strong charge is placed on the attractor electrodes 2024,2034 so as to draw some or all of the ions headed to the local detectorelectrode 2008, 2010 into the IMS drift tube 2021, 2031. For example,with detector electrode 2008 mildly negatively biased and attractorelectrode 2024 being more negatively biased, the ion flow splits withsome ions 17+ contacting electrode 2008 for generating DMS detectiondata and some ions flowing into the drift tube 2021.

The ions in the drift tube are propelled by a DC gradient established atelectrodes 2022, culminating with the ions driving into the morenegatively charged attractor electrode 2024 (which also serves as acollector or detector electrode). These ion strikes are detected and areprovided as IMS time-of-flight detection data which can be correlatedwith lookup tables of known species behavior.

But in a further embodiment of the invention, the DMS and IMS detectiondata are combined to provide improved species spectra separation andidentification. Now the DMS curve is anchored by addition of a dc offsetfrom the IMS data that is characteristic of the species being analyzed.To wit: the absolute mobility information associated with that detectedion species obtained by measuring the low field mobility value for thatspecies is combined with the differential mobility data for thatspecies. This anchors the mobility curve and results in a precisefingerprint for that species.

It will be further appreciated that in practice of the invention, it ispossible to provide positive and negative ion species separation anddetection simultaneously within the DMS apparatus and thensimultaneously in both IMS detectors. It will therefore be furtherappreciated that this compact apparatus can process complex samples inreal time with very useful species detections.

These above illustrative embodiments can be achieved by use ofconventional IMS devices attached to the orifices 2012, 2014. However,the embodiment of FIG. 12A may be provided in a compact and integratedpackage. Such package may also include a shutterless IMS as described oroptionally a more conventional IMS configuration having a control gate2026, 2036 in the drift tube as shown by dotted line in the figure.

FIG. 12B shows non-flat or non-straight flow path/electrodes which maybe incorporated into apparatus 2000. It will be further appreciated thatthe embodiment of FIG. 12 or similar arrangements may be provided in avariety of configuration which may include combined series and/orparallel DMS-IMS.

In yet a further embodiment of the invention of FIG. 12A, an ion trap2050 is defined which generates an electric field between electrodes2052, 2054 to drive hold positive or negative ions in the region of thedetector. This enables buildup of the sample which then is released intothe IMS as in the conventional shuttered IMS system.

Various illustrative examples of novel detection strategies in practiceof embodiments of the invention are disclosed herein. This discussionmay be applied to ions, particles, articles, biologicals, vehicles,people, things, or the like, and variations thereof; these also may bedescribed by alternative terms, such as “ions”, without limitation, andyet such breadth will be understood to be within the spirit and scope ofthe present invention.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

1. A method for identification of an unknown item in a sample travelingthrough an excitation field, the excitation field having a varyinginfluence upon the mobility behavior of the sample traveling theexcitation field, the method comprising the steps of: generating avarying excitation field; subjecting a sample to the excitation field,the sample having field-dependent mobility behavior that reflects fieldconditions, and the excitation field having sufficient strength tofragment the sample; subjecting the sample to a plurality of fieldconditions in the excitation field; compensating the plurality of fieldconditions to pass the unknown item through the excitation field; andidentifying the unknown item as a member of a known species, theidentification being based on known field-dependent mobility behavior ofthe known species in the plurality of compensated field conditions.
 2. Amethod as in claim 1 wherein the fragmenting produces positive andnegative ions.
 3. A method as in claim 2 comprising identifying thepositive and negative ions over a rage of compensation voltages.
 4. Amethod as in claim 1 comprising varying the excitation field to produceionized monomers.
 5. A method as in claim 1 wherein the plurality offield conditions are varied over a range of dispersion voltages toproduce multiple attributes of the field-dependent mobility behaviordependent on compensation voltage.
 6. A method as in claim 5 wherein themultiple attributes are peaks, and each of the peaks identifies aparticular ion.